The synthesis, structure, and reactivity of the osmium(IV) trihydrido silyl complex, OsH3(SiMe3)(CO)(PPh3)2

被引：19

作者：

Möhlen, M ^{[1
]}

Rickard, CEF ^{[1
]}

Roper, WR ^{[1
]}

Salter, DM ^{[1
]}

Wright, LJ ^{[1
]}

机构：

[1] Univ Auckland, Dept Chem, Auckland, New Zealand

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2000年 / 593卷

关键词：

hydride complexes; silyl complexes; osmium;

D O I：

10.1016/S0022-328X(99)00617-8

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction between the five coordinate complex, Os(Ph)Cl(CO)(PPh3)(2), and HSiMe3 produces the osmium(IV) trihydrido silyl complex, OsH3(SiMe3)(CO)(PPh3)(2) (1). The structure of 1 has been determined by single crystal X-ray crystallography and by multi-nuclear NMR spectroscopy. The structure has an approximately tetrahedral disposition of silyl, carbonyl and the two PPh3 ligands about osmium with the three classical hydride ligands located, one trans to CO, and the other two each approximately trails to a PPh3. Treatment of complex 1 with HSiR3 (R = Et, Ph), HSn(p-tolyl)(3), or HC2Ph gives OsH3(SiR3)(CO)(PPh3)(2) (R = Et (2), Ph (3)), OsH2[Sn(p-tolyl)(3)](2)(CO)(PPh3)(2) (4) or OsH(C2Ph)(CO)(PPh3)(3) (5), respectively A likely intermediate in these reactions is the coordinatively unsaturated complex, OsH2(CO)(PPh3)(2). (C) 2000 Elsevier science S.A. All rights reserved.

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页码：458 / 464

页数：7

相关论文

共 25 条

[1] SOME ASPECTS OF SILICON-TRANSITION-METAL CHEMISTRY [J].

AYLETT, BJ .

ADVANCES IN INORGANIC CHEMISTRY, 1982, 25 :1-133

[2] AN EMPIRICAL CORRECTION FOR ABSORPTION ANISOTROPY [J].

BLESSING, RH .

ACTA CRYSTALLOGRAPHICA SECTION A, 1995, 51 :33-38

[3] Oxidative addition of group 14 element hydrido compounds to OsH2(eta(2)-CH2=CHEt)-(CO)(P(i)Pr3)(2): Synthesis and characterization of the first trihydrido-silyl, trihydrido-germyl, and trihydrido-stannyl derivatives of osmium(IV) [J].

Buil, ML ;

Espinet, P ;

Esteruelas, MA ;

Lahoz, FJ ;

Lledos, A ;

MartinezIlarduya, JM ;

Maseras, F ;

Modrego, J ;

Onate, E ;

Oro, LA ;

Sola, E ;

Valero, C .

INORGANIC CHEMISTRY, 1996, 35 (05) :1250-1256

[4] OXIDATIVE ADDITION OF GROUP-14 HYDRIDES TO OSMIUM(O), OSMIUM(II) AND RUTHENIUM(O) COMPLEXES - CRYSTAL-STRUCTURES OF OS(SIET(3))H(CO)(2)(PPH(3))(2) AND OS(GE[P-TOLYL](3))H(CO)(2)(PPH(3))(2) [J].

CLARK, GR ;

FLOWER, KR ;

RICKARD, CEF ;

ROPER, WR ;

SALTER, DM ;

WRIGHT, LJ .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1993, 462 (1-2) :331-341

[5] COMPOUNDS WITH RUTHENIUM SILICON AND OSMIUM SILICON BONDS [J].

CLARK, GR ;

RICKARD, CEF ;

ROPER, WR ;

SALTER, DM ;

WRIGHT, LJ .

PURE AND APPLIED CHEMISTRY, 1990, 62 (06) :1039-1042

[6] Reactions of hydrosilanes with transition-metal complexes: Formation of stable transition-metal silyl compounds [J].

Corey, JY ;

Braddock-Wilking, J .

CHEMICAL REVIEWS, 1999, 99 (01) :175-292

[7] Intramolecular hydrogen site exchange in an HRu(SiHPh(2)) moiety [J].

Gusev, DG ;

Nadasdi, TT ;

Caulton, KG .

INORGANIC CHEMISTRY, 1996, 35 (23) :6772-6774

[8] AN NMR METHOD FOR DISTINGUISHING CLASSICAL FROM NONCLASSICAL STRUCTURES IN TRANSITION-METAL POLYHYDRIDES [J].

HAMILTON, DG ;

CRABTREE, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (13) :4126-4133

[9] ORGANOSILICON CHEMISTRY .27. SILYL-RUTHENIUM(IV) COMPLEXES [J].

HASZELDINE, RN ;

MALKIN, LS ;

PARISH, RV .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1979, 182 (03) :323-332

[10] The nature of the metal-silicon bond in [M(SiR3)H-3(PPh3)(3)] (M=Ru, Os) and the crystal structure of [Os{Si(N-pyrrolyl)(3)}H-3(PPh3)(3)] [J].

Hubler, K ;

Hubler, U ;

Roper, WR ;

Schwerdtfeger, P ;

Wright, LJ .

CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (10) :1608-1616